The Parisian club has now claimed the prestigious trophy on fourteen separate times.
The Parisian giants needed a stoppage-time equaliser followed by a successful spot-kick decider to overcome Marseille in Kuwait and secure a record-extending fourth consecutive French Super Cup victory.
The Champions League holders seemed to be sailing towards a comfortable win in the match between the French league winners and the Coupe de France winners after Ousmane Dembele found the net in the opening stages.
Yet, the southern French side fired two times late to seize a surprise advantage. First, the English forward converted from the spot-kick, before Willian Pacho unfortunately turned the ball into his own net for an own-goal.
In a breathtaking twist of events, Goncalo Ramos grabbed a crucial equaliser in the dying seconds to send the match into a deciding shootout. PSG goalkeeper Lucas Chevalier then emerged as the hero, stopping crucial attempts from Matt O'Riley and Hamed Traore.
From the spot, Ramos, the midfielder, the full-back, and the young talent all scored successfully for Paris Saint-Germain to seal a 4-1 shootout win.
The record winners PSG, who met last season's Ligue 1 second-placed team Marseille after achieving a domestic double, have now lifted this competition for the twelfth time in the past 13 years.